Preparation of alkaline earth fluorophosphate phosphors by coprecipitation



Patented July 19, 1949 UNITED STATES iili'r as or fliPiTA-Tli N fiernian Froelich, Cleveland oPHosrriA'rii PH ALKAL lNi: EARTH i ritosrnons BY COPRE- Heights, ohio, as-

salient-General Electric Company, a. corpora tion of New York switching, Application may 5, 1945,

, Serial No. 592,277

This invention ield "'5'; to l'ei' ric dils charge mb and i s wi gee elnamaem materials or phosphor's that are encitable to fluo rescence by the discharge or ra producedin h devices, i ,.ii f il flY-1 asil l min s or fluorescent materials andthein preparation. The invention is applic'able to thepreparation of fluorescent compositions of metal halophosphate matrices a nd activating metals, and is hereinafter explained in detail inconnection with the activated alkaline earthmetal halophosphates disclosed in U, application Serial,,No. 5 38;559 of Alfred H. M' Keag, and P ter-W, R bbi, filed J1me 1944, how a ia o est nd assi ned to the assignee o f-this' application Besides afiorde ing a more convenientand advantageous method 9f preparing these phosp ors, my invention has yielded products of superior luminescent brightness' In general; e-re e nes ares-9 11 2 5 more. or less ah l ld j tit e-latera mi al apatite, and are supbosedlto be represented by a formula such as 3MP04l2j1lllfl a where L represents a halogen er n m ted: halogens, and M and M represent either different or identical bivalent metals or mixtures of such rnetals. I-Ialophosphat'es here especially in question are artificial substsn'c'esreomppanq or complexes) comprising as esseiitiaLlattice constituents one or more bivalent: Groupll metals, the phosphate radical (P04), and one or more halogens, and having a lattice structure similarto that of apatite, i. e., a structurewhose difference from that of apatiteis e greaterthanmight be expected to result (a) from thepartial orcomplete substitution of another alkalineearth metal or another halogen forthoselound inapatite, or (b) from the introductionefan activator. In some cases, the lattice structure of such phosphors may also include oiiidfisl of suchmetal. Generally speaking, artificial, halo-phosphates are most suitable as phosphorswhen at least half of the bivalentlnetal atom s are alkaline earth metals of the group comprising calciumand strontium (i. e., calcium or strontlurn atoms), while at least half of th halo'gen atoms are of the group comprising fiuorinei, chlorine, or bromine (i. e., fluorine atoms, v or chlorine atoms, or bromine atoms, or a miiitu fe of atoms of two or more of thesethr haldgensj jthis halo-phosphate being activated by. n a'ctivator whereof part at least ispreferably antimony though if desired antimony ay be replaced partly or wholly with bismuth the activator, or with tin or lead. Several act of this character may be used't' ether, s for egample,

' bismuth lead ldjtii l; andsuch antimony and activating metal of'the d t s p and 11th series ntimony, bis-' tenses; (01. 2524014) r 2 of the Periodic System) niay'be supplemented with manganese, as explainedhereinafter, w The proportion of activating antimony'can be varied within wide limits, say from' per cent to lo per cent by weight, Without any great change in the luminescent properties ofthe material; but proportionsmuch outside this range decrease the luminescent eliiciency. In general; the optimum proportion; is usually within a range of 2 to 6 per cent. Thecolor of the light under 2537A. excitation is a pale blue not very diiierent from that of magnesium tungstate,v or even a green blue in some cases.

When bismuth wholly or' partially 'replacesane timony, the proportion of activating bismuth should generally be greater than the amount of antimony replaced; thus while 2 to 6 per cent of antimony is preferred,- the preferred amountv of bismuth when no antimon is,, present maybe as high as 7 /2 per cent. Suitable proportionszo'f tin and of lead are 4 per cent and 15 pericent respectively, with either of which may be used 2% per cent manganese as a supplementalactivator.

In general, indeed, halophosphat'e, phosphors may, contain manganese along with the primary activator(s) aboveindicated. In fact, one of the most advantageous features of luminescent materials activated with antimony or other metal(s) according to the invention isthe wide range of color through which the lightprod-uced can be varied by varying the proportion of supplemental manganese employed. In general, iiicreasing percentages of manganese with anti mony increase the wavelength of the dominant hue from pale blue or green-blue through cream to white with a yellowish, pinkish, ororange tinge to yellow, orange, or even red; lead, likewise, increasing amounts of supplemem tal manganese from zero up to a limit commonly less than 10 per cent generally shift the color of the luminescent light towardred, and usually increase its intensity. With bismuth, however, the effect of supplemental manganese is rather different: it often produces little or no'chang in color, but it may increase the "emciency of hi minescence appreciably. But while manganese is thus valuable as a modifying or supplemental activator, it is doubtful whether it should be considered a primary activator, since under ex citation of halo-phosphate by 2537A. radiation, at any rate, manganese without other activator produces little if any luminescence;

The starting materials for the preparation of With tin and.

bought; bntgit m-ust dry chlorides and;

but must be taken into account in determining the amount of halide M'Lz that is actually introduced. Water used in preparing or washing intermediate products or the final phosphor should generally be distilled water. 7

To produce activated alkaline earth metal halophosphate phosphor according to my invention, an intimate mixture comprising halide and phosphate of such metal and phosphate of desired activating metal is heated to a sufficient temperature to synthesize the halophosphate matrix and to bring the activating metal into activating relation with this matrix, for it is metal atoms that activate the matrix, rather than the compound thereof in the mixture, or even that in the phosphor itself. Suitable temperatures are from about 1000 0. ct 1150 C., with a general preference for temperatures nearer 1000" C. than 1150 0.; though for phosphors comprising tin or lead as activators, around 1100 C. may be preferred. In preparing fiuorophosphate phosphors, especially, I precipitate halide and phosphate components of such mixture together from a common solution of soluble compound of alkaline earth metal, and segregate the resulting halide and phosphate in intermixture from the residual solution. The dim-culty in assuring that the alkaline earth metal phosphate thus precipitated shall consist essentially or entirely of the desired normal orthophosphate for forming the halophosphate may be practically obviated by afterward mixing with the segregated mixture sufiicient alkaline earth metal compound to convert the undesired other phosphate of the precipitate to normal orthophosphate during heatin of the total mixture to form the phosphor, as above mentioned.

The preferred procedure in effecting precipitation as just outlined is to add to a solution of alkaline earth metal compound the other component materials employed in liquid dispersion, i. e., in solution or suspension. To obviate any undesired reactions that might occur amongst these other components if themselves brought together before addition to the solution of alkaline earth metal compound, and might interfere with or prevent the desired reactions, some or all of these other components may be added in separate solutions or suspensions.

As a concrete illustration of my invention for the assistance of those desiring to practice it, but not as defining or limiting the invention in its broader aspects, I shall now describe in detail the production of a calcium fiuorophosphate acti vated with antimony and maganese.

Dissolve 240 grams calcium nitrate,

Ca(NO3) 2-4H2O in 700 cc. of water, and bring the solution to a boil. To this add a hot solution (e. g., at 60 C.)

of 11.5 grams ammonium fluoride, NHiF, forming a colloidal precipitate of calcium fluoride, Next add segregate the mixed precipitate from the resid-' ual solution or liquid. The precipitate is thoroughly washed with water on a suction filter, dried at about 200 C., and crushed to a fairly fine powder. This is mixed with 50 grams of calcium carbonate, CaCOa, and the total mixture is ball-milled for say half an hour, or sifted several times through a mesh sieve, in order to assure thorough intermixture of all the components, as well as freedom from lumps or coarse particles It is then ready for heating or firing.

For this purpose, the mixture may be placed in a quartz tube and heated in an electric tube furnace at about 1050 to 1100 C. for about half an hour, in an atmosphere of inert gas, particularly dry nitrogen, continually passing through the quartz tube. The temperature of firing may approach as nearly as feasible to that at which the mixture begins to sinter, but should never get high enough to melt the mix. After cooling off in the nitrogen atmosphere, the product is crushed and ball-milled or sifted as beforefiring, thoroughly washed with water, and dried at about C., when it is ready for use.

The proportions in the foregoing description represent an excess of some 20 to 30% of CaF over the approximate 3 to 1 mol ratio of Caa(PO4) 2 and CaFz in a true halophosphate such as natural apatite, and also an excess of CaCOs which renders the fiuorophosphate slightly basic. These excesses correspond to those in the corresponding fiuorophosphate phosphor disclosed in the McKee-g and Ranby application, and are practically unavoidable in producing a fluorophosphate as there described, since without them a stoichiometric fluorophosphate does not form. But too much excess CaCOa tends to cause disintegration of the phosphor, while the excess CaFz undesirably fluxes the mixture in firing, so that the latter tends to sinter or melt rather easily.

With the method of precipitating the calcium fluoride and phosphate from a common solution as described above, however, the excess CaFz and CaCOa can be avoided, and other advantages secured. When the calcium phosphate is precipitated in the presence of the colloidally suspended CaF2, which is itself too fine to be filtered out of the solution, the fine CaFz particles are as it were adsorbed on the filterable particles of calcium phosphate, so that there is no difiiculty in afterward filtering the CaFz out of the solution. Highly reactive on account of its fineness, and in the most intimate intermixture and contact with the calcium phosphate, no excess of Cal 'z or of CaCOa over stoichiometric proportions is needed to assure formation of a stoichiometric halophosphate. Accordingly, the amount of NHiF addedto the calcium nitrate solution as above described may be reduced to 9.2 grams instead of 11.5, and the amount of CaCOa mixed with the precipitates before firing may be reduced to 40 grams instead of 50.

By firing the total mixture in an inert atmos- A phere, a single firing sufi'ices, as against the double firing with intermediate grinding that is described in the McKeag and Ranby application. In the case ofhalophosphate containing manganese, the nitrogen atmosphere or the like also prevents the formation in the phosphor of manganic phosphate or other compound in which manganese is more than divalent; and so the phosphor fiuoresces more brightly. .Manganic phosphates form rather readily in oxygen or air at the firing temperatures above indicated, or

even during the cooling of the product from around 1100 C. down to ambient or ordinary room temperature of some 20 0., and they not only reduce the fluorescence of the product, but tend to give it a purple tinge when the unexcited phosphor is looked at by ordinary daylight. Even when the material is heated or fired in air, some improvement of the color and fluorescent brightness of the product is obtained by transferring it at top temperature to an atmosphere of nitrogen and letting it cool down in the nitrogen.

Both the main improvements hereinbefore described (coprecipitation, and firing in an inert environment) are applicable to halophosphates activated with the other metals mentioned above (bismuth, tin, or lead), as well as to halophosphates whose alkaline earth metal comprises strontium.

What I claim as new and desire to secure by Letters Patent of the United States is:

1. The method of preparing fluorescent alkaline earth metal fluorophosphate which comprises preparing an aqueous solution of a water-soluble alkaline earth metal salt, adding thereto a volatile water soluble inorganic fluoride which reacts with part of the said alkaline earth metal and forms therewith an insoluble fluoride, adding an aqueous dispersion of compound of at least one activator metal of the group consisting of antimony, bismuth, tin and lead and mixtures of at least one said metal with manganese, adding a water soluble inorganic phosphate compound which will react with further amounts of the said alkaline earth metal to precipitate a phosphate thereof and bring down therewith the said insoluble alkaline earth metal fluoride and compound of said activator metal, drying and crushing the resultant precipitate to a fine powder, mixing the said powder with sufficient carbonate of said alkaline earth metal to give the corresponding orthophosphate upon ignition, and firing the mixture at a temperature of approximately 1000-1l50 C.

2. The method of preparing fluorescent alkaline earth metal fluorophosphate which comprises the steps of preparing an aqueous solution of alkaline earth metal nitrate, adding thereto ammonium fluoride to react with part of said alkaline earth metal and form therewith an insoluble fluoride, adding an aqueous dispersion of compound of at least one activator metal of the group consisting of antimony, bismuth, tin and lead and mixtures of at least one said metal with manganese, adding thereto ammonium phosphate to precipitate a phosphate of said alkaline earth metal and bring down therewith the said insoluble alkaline earth metal fluoride and compound of said activator metal, filtering the resultant mixture, drying and crushing the filtrate to a fine powder, and firing the mixture at a temperature of approximately 1000-1150 c,

3. The method of preparing fluorescent alkaline earth metal fluorophosphate which comprises the steps of preparing an aqueous solution of alkaline earth metal nitrate, adding thereto ammonium fluoride to react with part of said alkaline earth metal and form therewith an insoluble fluoride, adding an aqueous dispersion of compounds of at least one main activator metal of the group consisting of antimony, bismuth, tin and lead together with supplemental manganese, adding thereto ammonium phosphate to react with further amounts of the said alkaline earth metal and with said manganese compound to precipitate phosphates thereof and bring down therewith the said insoluble earth metal fluoride and compound of said main activator metal, drying and crushing the resultant precipitate to a fine powder, mixing the said powder with sufiicient carbonate of said alkaline earth metal to give the corresponding orthophosphate upon ignition; and firing the mixture at a temperature of approximately 1000-1150 C. in an atmosphere of nitrogen.

1. The method of preparing fluorescent alkaline earth metal fluorophosphate which comprises the steps of preparing an aqueous solution of an alkaline earth metal nitrate, adding thereto ammonium fluoride to react with part of said alkaline earth metal and form therewith an insoluble fluoride, adding an aqueous suspension of antimony oxide and a solution of manganese nitrate as activator compounds, adding ammonium phosphate to react with further amounts of the said alkaline earth metal and with the said manganese nitrate to precipitate a manganese phosphate and phosphate of the said alkaline earth metal and bring down therewith said insoluble fluoride and said antimony oxide, drying and crushing the resultant precipitate to a flne powder, mixing the said powder with sufiicient carbonate of said alkaline earth metal to give the corresponding orthophosphate upon ignition, and firing the mixture at a temperature of approximately 1000115 C. in an atmosphere of nitrogen.

5. The method of preparing fluorescent calcium fluorophosphate which comprises reacting the following ingredients in approximately the proportions stated; dissolving 240 g. calcium nitrate (4H2O) in 700 cc. of water, adding a hot solution of 9-115 g. of NH4F to form colloidal CaF2, adding an aqueous suspension of 4 g. of SbzOs and about 15 to 25 cc. of manganese nitrate solution, adding a hot solution of g. of (NH4)2HPO4 in 700 cc. of water, shaking and filtering the mixture as soon as the precipitate has become crystalline, drying and crushing the filtrate to a fairly fine powder mixing the said powder with 40-50 g. of CaCOs, and firing the mixture at a temperature of approximately 1000-1150 C. in an atmosphere of nitrogen.

. HERMAN C. FROELICH.

REFERENCES CITED The following referenlces are of record in the Mellor, Comprehensive Treatise on Inorganic and Theoretical Chemistry, vol. III, pages 896- 8 8. 

